Insecticidal fertilizer mixtures

ABSTRACT

The present invention relates to insecticidal fertilizer mixtures comprising a fertilizer component and an agonist or antagonist of the nicotinergic acetylcholine receptors of insects.

The present invention relates to insecticidal fertilizer mixturescomprising a fertilizing component and an agonist or antagonist ofnicotinergic acetylcholine receptors of insects, and to their use.

Agonists or antagonists of the nicotinergic acetylcholine receptors ofinsects are known, for example, from the following publications:

European offenlegungsschriften Nos. 464 830, 428 941, 425 978, 386 565,383 091, 375 907, 364 844, 315 826, 259 738, 254 859, 235 725, 212 600,192 060, 163 855, 154 178, 136 636, 303 570, 302 833, 306 696, 189 972,455 000, 135 956, 471 372, 302 389; German Offenlegungsschriften Nos. 3639 877, 3 712 307; Japanese Offenlegungsschriften Nos. 03 220 176, 02207 083, 63 307 857, 63 287 764, 03 246 283, 04 9371, 03 279 359, 03 255072; U.S. Pat. Nos. 5,034,524, 4,948,798, 4,918,086, 5,039,686,5,034,404; PCT Applications Nos. WO 91/17,659, 91/4965; FrenchApplication No. 2 611 114; Brazilian Application No. 88 03 621.

Reference is hereby made expressly to the methods, processes, formulaeand definitions described in these publications and to the individualpreparations and compounds described therein.

It is known to employ fertilizers for ornamental houseplants in the formof small fertilizer sticks.

It is also known to employ insecticides for ornamental houseplants inthe form of impregnated cardboard strips which are pressed into thenutrient substrate of the plant.

Also known for keeping ornamental houseplants is a tablet which containsdimethoate as insecticidal active substance and fertilizer as carriermaterial. The action of this mixture, however, is not completelysatisfactory.

The present invention relates to:

1. Dimensionally stable mixtures of agonists or antagonists of thenicotinergic acetylcholine receptors of insects with fertilizers,adhesives and optionally auxiliaries and carrier materials in the formof small sticks, plates, tablets or granules.

2. Processes for increasing the action of agonists or antagonists of thenicotinergic acetylcholine receptors of insects, characterized in thatthey are employed in the form of dimensionally stable mixtures withfertilizers, adhesives and optionally auxiliaries and carrier materials.

3. Processes for the preparation of dimensionally stable mixtures ofagonists or antagonists of the nicotinergic acetylcholine receptors ofinsects with fertilizers, characterized in that they are mixed withadhesives and optionally with auxiliaries and carrier materials and arecompressed or extruded to the desired form.

4. Use of dimensionally stable mixtures of agonists or antagonists,fertilizers, adhesives and optionally auxiliaries and carrier materialsfor the long-term protection of plants against insect damage, byincorporating these mixtures into the nutrient medium of the plants.

The action of the agonists or antagonists of the nicotinergicacetylcholine receptors of insects in the mixtures according to theinvention begins more rapidly and persists for longer than that of thecustomary fertilizer-free granules. The mixtures according to theinvention can be employed simply and without problems, specifically innon-commercial horticulture.

Some agonists or antagonists of the nicotinergic acetylcholine receptorsof insects are covered by the class of nitromethylenes and relatedcompounds.

These compounds can be represented preferably by the general formula (I)##STR1## in which R represents hydrogen or optionally substitutedradicals from the group acyl, alkyl, aryl, aralkyl, heteroaryl orheteroarylalkyl;

A represents a monofunctional group from the series consisting ofhydrogen, acyl, alkyl, aryl or represents a bifunctional group which islinked to the radical Z;

E represents an electron-withdrawing radical;

X represents the radicals --CH═ or ═N--, it being possible for theradical --CH═ to be linked to the radical Z instead of one H atom;

Z represents a monofunctional group from the series consisting of alkyl,--O--R, --S--R, ##STR2## or represents a bifunctional group which islinked to the radical A or to the radical X.

Particularly preferred compounds of the formula (I) are those in whichthe radicals have the following meaning:

R represents hydrogen and represents optionally substituted radicalsfrom the series consisting of acyl, alkyl, aryl, aralkyl, heteroaryl,heteroarylalkyl.

Acyl radicals which may be mentioned are formyl, alkylcarbonyl,arylcarbonyl, alkylsulphonyl, arylsulphonyl,(alkyl-)-(aryl-)-phosphoryl, which may in turn be substituted.

Alkyl which may be mentioned is C₁₋₁₀ -alkyl, in particular C₁₋₄ -alkyl,specifically methyl, ethyl, i-propyl, sec.- or t.-butyl, which may inturn be substituted.

Aryl which may be mentioned is phenyl, naphthyl, especially phenyl.

Aralkyl which may be mentioned is phenylmethyl, phenethyl.

Heteroaryl which may be mentioned is heteroaryl having up to 10 ringatoms and N, O, S, in particular N as heteroatoms. Thiophenyl, furyl,thiazolyl, imidazolyl, pyridyl, benzothiazolyl may be mentionedspecifically.

Heteroarylalkyl which may be mentioned is heteroarylmethyl,heteroarylethyl having up to 6 ring atoms and N, O, S, in particular N,as heteroatoms.

Substituents which may be listed by way of example and preference are:alkyl having preferably 1 to 4, in particular 1 or 2, carbon atoms, suchas methyl, ethyl, n- and i-propyl and n-, i- and t-butyl; alkoxy havingpreferably 1 to 4, in particular 1 or 2, carbon atoms, such as methoxy,ethoxy, n- and i-propyloxy and n-, i- and t-butyloxy; alkylthio havingpreferably 1 to 4, in particular 1 or 2, carbon atoms, such asmethylthio, ethylthio, n- and i-propylthio and n-, i- and t-butylthio;halogenoalkyl having preferably 1 to 4, in particular 1 or 2, carbonatoms, and preferably 1 to 5, in particular 1 to 3, halogen atoms, thehalogen atoms being identical or different and the halogen atomspreferably being fluorine, chlorine or bromine, in particular fluorine,such as trifluoromethyl; hydroxyl; halogen, preferably fluorine,chlorine, bromine and iodine, in particular fluorine, chlorine andbromine; cyano; nitro; amino; monoalkyl- and dialkylamino havingpreferably 1 to 4, in particular 1 or 2 carbon atoms per alkyl group,such as methylamino, methyl-ethyl-amino, n- and i-propylamino andmethyl-n-butylamino; carboxyl; carboalkoxy having preferably 2 to 4, inparticular 2 or 3 carbon atoms, such as carbomethoxy and carboethoxy;sulpho (--SO₃ H); alkylsulphonyl having preferably 1 to 4, in particular1 or 2, carbon atoms, such as methylsulphonyl and ethylsulphonyl;arylsulphonyl having preferably 6 or 10 aryl carbon atoms, such asphenylsulphonyl, and heteroarylamino and heteroarylalkylamino, such aschloropyridylamino and chloropyridylmethylamino.

A particularly preferably represents hydrogen and represents optionallysubstituted radicals from the series consisting of acyl, alkyl, aryl,which preferably have the meanings given for R. A additionallyrepresents a bifunctional group. Optionally substituted alkylene having1-4, in particular 1-2, C atoms may be mentioned, substituents which maybe mentioned being the substituents listed further above, and it beingpossible for the alkylene groups to be interrupted by heteroatoms fromthe series consisting of N, O, S.

A and Z may form, together with the atoms to which they are attached, asaturated or unsaturated heterocyclic ring. The heterocyclic ring maycontain a further 1 or 2 identical or different heteroatoms and/orhetero groups. The heteroatoms are preferably oxygen, sulphur ornitrogen and the hetero groups are preferably N-alkyl, the alkyl of theN-alkyl group preferably containing 1 to 4, in particular 1 or 2, carbonatoms. Alkyl which may be mentioned is methyl, ethyl, n- and i-propyland n-, i- and t-butyl. The heterocyclic ring contains 5 to 7,preferably 5 or 6, ring members.

Examples which may be mentioned of the heterocyclic ring arepyrrolidine, piperidine, piperazine, hexamethyleneimine,hexahydro-1,3,5-triazine, morpholine, which may optionally besubstituted preferably by methyl.

E represents an electron-withdrawing radical, particular mention beingmade of NO₂, CN, halogenoalkylcarbonyl such as 1,5-halogeno-C₁₋₆-carbonyl, in particular COCF₃.

X represents --CH═ or --N═

Z represents optionally substituted radicals alkyl, --OR, --SR, --NRR,where R and the substituents preferably have the meaning given above.

Z is able to form, apart from the abovementioned ring, together with theatom to which it is attached and the radical ##STR3## in the place of X,a saturated or unsaturated heterocyclic ring. The heterocyclic ring maycontain a further 1 or 2 identical or different heteroatoms and/orhetero groups. Heteroatoms are preferably oxygen, sulphur or nitrogenand hetero groups are preferably N-alkyl, the alkyl or N-alkyl grouppreferably containing 1 to 4, in particular 1 or 2, carbon atoms. Alkylwhich may be mentioned is methyl, ethyl, n- and i-propyl and n-, i-, andt-butyl. The heterocyclic ring contains 5 to 7, preferably 5 or 6, ringmembers.

Examples which may be mentioned of the heterocyclic ring arepyrrolidine, piperidine, piperazine, hexamethyleneimine, morpholine andN-methylpiperazine.

Compounds which may be mentioned and which it is possible to use withvery particular preference in accordance with the invention arecompounds of the general formulae (II) and (III): ##STR4## in which nrepresents 1 or 2,

Subst. represents one of the substituents listed above, in particularhalogen and very particularly chlorine,

A, Z, X and E have the meanings given above,

The following compounds may be mentioned specifically: ##STR5##

The contents of active substance are between 0.01 to 10%, in particularbetween 0.1 to 2.5%.

Fertilizer components which may be used are organic and inorganicnitrogen-containing compounds such as urea, urea-formaldehydecondensation products, amino acids, ammonium salts and nitrates, andalso potassium salts (preferably chlorides, sulphates, nitrates) andphosphoric acid and/or salts of phosphoric acids (preferably potassiumsalts and ammonium salts). The fertilizers may also contain salts ofmicronutrients (preferably manganese, magnesium, iron, boron, copper,zinc, molybdenum and cobalt) and phytohormones (e.g. vitamin B1 andindole-III-acetic acid). The commercially available complete fertilizersare preferably employed.

The principal fertilizer constituents, nitrogen, potassium andphosphorus, can be varied within wide limits. It is conventional to usecontents of from 1 to 30% of nitrogen (preferably from 5 to 20%), from 1to 20% of potassium (preferably from 3 to 15%) and from 1 to 20% ofphosphorus (preferably from 3 to 10%). The contents of microelements areusually in the ppm range, preferably from 1 to 1000 ppm.

Adhesives which may be mentioned are tackifiers such ascarboxymethylcellulose, natural and synthetic polymers in the form ofpowders, granules or latices, polyvinylpyrrolidone,vinylpyrrolidone-styrene copolymers, vinylpyrrolidon-vinylacetatcopolymers, polyethyleneglycols or inorganic adhesives such as gypsum orcement. They are present in the mixture in concentrations of from 1 to30% by weight, preferably from 2 to 20% by weight.

Suitable solid carrier materials are, for example, natural groundminerals such as kaolins, aluminas, talc, chalk, quartz, attapulgite,montmorillonite or diatomaceous earth and synthetic ground minerals suchas highly dispersed silicic acid, aluminium oxide and silicates, inaddition calcium-phosphates and calcium-hydrogen-phosphates. Suitablesolid carrier materials for granules are, for example, crushed andfractionated natural minerals such as calcite, marble, pumice,sepiolite, dolomite and synthetic granules of inorganic and organicground materials, and also granules of organic material such as sawdust,coconut husks, corn cobs and tobacco stalks.

Further auxiliaries for the preparation of the mixtures according to theinvention are disintegrants and surfactants.

Disintegrants are employed in order to promote the release of the activesubstance in the soil. Corn starch, crosslinked polyvinylpyrrolidone andspecific celluloses are used individually or in combination. Thedisintegrants are present in concentrations of from 1 to 20% by weight,preferably from 3 to 10% by weight.

Surfactants are employed in order to improve the biological activity ofthe active substance by solubilization; their content is between 1 to10% by weight, preferably from 2 to 5% by weight. Nonionic surfactantsof the alkyl-aryl-ethoxylate type are appropriate.

The mixtures of active substance, fertilizers, adhesive, auxiliary andinert substances are mixed intensively and compressed by an extruderinto small sticks with a diameter of from 3 to 10 mm, preferably from 6to 8 mm, and a length of from 1 to 10 cm, preferably from 3 to 6 cm.Alternatively, the mixture can be brought into the desired form of smallsticks using a tableting press. It is also possible first of all toproduce small sticks or tablets which are free from active substance andto coat these sticks or tablets, in a second step, with a solution ofthe active substance. This subsequent coating operation can also be usedwith advantage to apply active substance to fertilizer granules.

EXAMPLES

A mixture of

1.

0.25% imidacloprid

2.40% pyrrolidone-styrene copolymer

2.30% tristyrylphenyl 16-ethoxylate

0.80% talc A

5.00% corn starch

38.00% Triabon complete fertilizer (BASF)

40.00% kaolin

about 11.00% water

is thoroughly mixed in a kneading apparatus and then compressed in anextruder to give small sticks with a diameter of about 6 mm which arecut to a length of about 4 cm. After drying (40° C., 6 hours) the smallsticks have the desired strength.

2.

2.5% imidacloprid

4.8% pyrrolidone-styrene copolymer

2.3% tristyrylphenyl 16-ethoxylate

0.8% talc

5.0% corn starch

36.0% Nitrophoska-permanent complete fertilizer

38.0% kaolin

about 11.0% water

Preparation as for Example 1.

3. A mixture like Example 1 or 2 is brought without water into thedesired form, in a tableting press.

4. The complete fertilizers Triabon and Nitrophoska-permanent,respectively, in commercially available granulated form, are sprayed ina gravity mixer with a solution of imidocloprid in acetone, and dried.The active substance is located on the granule surface.

The fertilizer mixtures according to the invention are suitable for thecontrol of insects which are encountered in horticulture, in agricultureand in forests. They are active against normally sensitive and resistantspecies and against all or individual stages of development. Theabovementioned pests include:

From the order of the Isopoda, for example Oniscus asellus,Armadillidium vulgare and Porecellio scaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus.

From the order of the Chilopoda, for example, Geophilus carpophagus andScutigera spec.

From the order of the Thysanura, for example, Lepisma saccharina.

From the order of the Collembola, for example, Onychiurus armatus.

From the order of the Orthoptera, for example, Blatta orientalis,Periplaneta americana, Leucophaea maderae, Blattella germanica, Achetadomesticus, Gryllotalpa spp., Locusta migratoria migratorioides,Melanoplus differentialis and Schistocerca gregaria.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example Reticulitermes spp.

From the order of the Mallophaga, for example, Trichodectes spp. andDamalinea spp.

From the order of the Thysanoptera, for example, Hercinothrips femoralisand Thrips tabaci.

From the order of the Heteroptera, for example, Eurygaster spp.,Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodniusprolixus and Triatoma spp.

From the order of the Homoptera, for example, Aleurodes brassicae,Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicorynebrassicae, Cryptomyzus ribis, Aphis fabae, Doralis pomi, Eriosomalanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp.,Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus,Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphaxstriatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotushederae, Pseudococcus spp. and Psylla spp.

From the order of the Lepidoptera, for example, Pectinophoragossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletisblancardella, Hyponomeuta padella, Plutella maculipennis, malacosomaneustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrixthurberiella, Phyllocnistis citrella, Agrotis spp., Spodoptera exigua,Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp.,Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyraustanubilalis, Ephestia kuehniella, Galleria mellonella, Tineolabisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoeciapodana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella,Homona magnanima and Tortrix viridana.

From the order of the Coleoptera, for example, Anobium punctatum,Rhizopertha dominica, Acanthoscelides obtectus, Acanthoscelidesobtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsadecemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodeschrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilussurinamensis, Anthonomus pp., Sitophilus spp., Otiorrhynchus sulcatus,Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica,Dermestes spp., Trogoderma spp., Anthrenus spp. , Attagenus spp., Lyctusspp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbiumpsylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderusspp., Melolontha melolontha, Amphimallon solstitialis and Costelytrazealandica.

From the order of the Hymenoptera, for example, Diprion spp., Hoplocampaspp., Lasius spp., Monomorium pharaonis and Vespa spp.

From the order of the Diptera, for example, Aedes spp., Anopheles spp.,Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphoraerythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp.,Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp.,Hypoderma spp., Tanaus spp., Tannia spp., Bibio hortulanus, Oscinellafrit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleaeand Tipula paludosa.

Particularly worthy of mention is the action against aphids and whiteflyin market gardening and non-commercial horticulture.

The shaped articles according to the invention are employed in a dosesuch that, per liter of treated earth or nutrient medium, from about 1to 2000 mg of active substance, preferably from 1 to 100 mg of activesubstance and particularly preferably from 1 to 50 mg of activesubstance are employed.

EXAMPLE

10 poinsettia plants which were heavily infested with whitefly weretreated with different formulations of the active substanceimidacloprid. The action was observed 18 to 70 days after the treatment.The following treatments are carried out:

A: Imidacloprid granules, 5%, in a dose of 50 mg/l of earth, wereincorporated into the surface of the planted earth.

B: Imidacloprid granules, 5%, in a dose of 25 mg/l of earth, wereincorporated into the surface of the planted earth.

C: Imidacloprid granules, 5%, in a dose of 5 mg/l of earth, wereincorporated into the surface of the planted earth.

D: Small Triabon sticks with 2.5% of imidacloprid of composition 1(above) were stuck into the planted earth in a dose of 50 mg/l of earth.

E: Small Triabon sticks with 2.5% of imidacloprid of composition 1(above) were stuck into the planted earth in a dose of 25 mg/l of earth.

F: Small Triabon sticks with 2.5% of imidacloprid of composition 1(above) were stuck into the planted earth in a dose of 5 mg/l of earth.

The following results were obtained:

    ______________________________________                                                 Result after days in % action compared                                        with the untreated control                                           Treatment  18    22      28   42     49   70                                  ______________________________________                                        A          22    85      100  100    100  100                                 B          14    76      100  100    100  100                                 C          13    56      60   75     79   95                                  D          9     78      100  100    100  100                                 E          4     64      100  100    100  100                                 F          0     52      98   100    100  100                                 ______________________________________                                    

100% denotes complete action, 0% denotes no action.

We claim:
 1. An insecticidal fertilizer mixture comprising:(a) anagonist or antagonist of the nicotinergic acetylcholine receptor of aninsect; (b) a fertilizer; and (c) an adhesive;said mixture being in theform of a stick, plate, tablet or granule.
 2. The mixture according toclaim 1 wherein said agonist or antagonist is a compound of formula (I)##STR6## in which R represents hydrogen or optionally substitutedradicals from the group acyl, alkyl, aryl, aralkyl, heteroaryl orheteroarylalkyl;A represents a monofunctional group selected from thegroup consisting of hydrogen, acyl, alky, and aryl or represents abifunctional group which is linked to the radical Z; E represents anelectron-withdrawing radical; X represents the radicals --CH═ or ═N--,wherein the radical --CH═ may be linked to the radical Z instead of oneH atom; Z represents a monofunctional group selected from the groupconsisting of alkyl, --O--R, --S--R, and ##STR7## or represents abifunctional group which is linked to the radical A or to the radical X.3. The mixture according to claim 2 wherein said agonist or antagonistis a compound of formula (I) whereinR represents hydrogen and representsoptionally substituted radicals selected from the group consisting ofacyl, alkyl, aryl, aralkyl, heteroaryl, and heteroarylalkyl whereinAcylradicals are formyl, alkylcarbonyl, arylcarbonyl, alkylsulphonyl,arylsulphonyl, or (alkyl-)-(aryl-)-phosphoryl, which may be substituted;Alkyl radicals are C₁₋₁₀ -alkyl, which may be substituted; Aryl isphenyl or naphthyl; Aralkyl is phenylmethyl, or phenethyl; Heteroaryl isheteroaryl having up to 10 ring atoms and N, O, S as heteroatoms;Heteroarylalkyl is hetero-arylmethyl, or heteroarylethyl having up to 6ring atoms and N, O, S as heteroatoms;wherein the substitutions in theacyl radicals and alkyl radicals are C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄alkylthio, C₁ -C₄ halogenoalkyl, the halogen atoms being identical ordifferent and the halogen atoms being fluorine, chlorine and bromine;hydroxyl; halogen; cyano; nitro; amino; C₁ -C₄ monoalkyl- and C₁ -C₄dialkylamino; carboxyl; C₂ -C₄ carboalkoxy; C₁ -C₄ alkylsulphonyl; C₆-C₁₀ arylsulphonyl; and heteroarylamino and heteroarylalkylamino; Arepresents hydrogen and represents optionally substituted radicals fromthe series consisting of acyl, alkyl, and aryl; A and Z may form,together with the atoms to which they are attached, a saturated orunsaturated heterocyclic ring comprising 1 or 2 identical or differentheteroatoms or hetero groups, wherein the heteroatoms are oxygen,sulphur or nitrogen and the heterogroups are C₂ -C₄ N-alkyl; whereinalkyl is methyl, ethyl, n- and i-propyl and n-, i- and t-butyl; whereinthe heterocyclic ring comprises 5 to 7 ring members; E represents anelectron-withdrawing radical, selected from the group consisting of NO₂,CN, and alkylcarbonyl; X represents --CH═ or --N═; Z representsoptionally substituted radicals alkyl, --OR, --SR, or --NRR, wherein Rand the substitutions have the meanings given above; and Z is able toform, apart from the abovementioned ring, together with the atom towhich it is attached and the radical ##STR8## in the place of X, asaturated or unsaturated heterocyclic ring which may contain 1 or 2identical or different heteroatoms or hetero groups, wherein theheteroatoms are oxygen, sulphur or nitrogen and hetero groups are C₂ -C₄N-alkyl and wherein the heterocyclic ring contains 5 to 7 ring members.4. The mixture according to claim 2 wherein said agonist or antagonistis a compound of formula (II) ##STR9## in which n represents 1 or2,Subst. has the meaning given above in claim 2 for subsitutions; and A,Z, X and E have the meanings given above in claim
 2. 5. The mixtureaccording to claim 1 wherein said agonist or antagonist is a compoundselected from the group consisting of ##STR10##
 6. A process for thepreparation of an insecticidal fertilizer mixture comprising (a) mixingan agonist or antagonist of the nicotinergic acetylcholine receptor ofan insect with a fertilizer and an adhesive and optionally addingdisintegrants and surfactants and carriers, and (b) compressing orextruding said mixture into a desired form.
 7. A method for theprotection of plants from unwanted insects which comprises adding aninsecticidally effective amount of the mixture according to claim 1 intothe nutrient medium of such plants.
 8. An insecticidal fertilizermixture comprising:(a) a compound of the formula ##STR11## (b) afertilizer; and (c) an adhesive;said mixture being in the form of astick, plate, tablet or granule.
 9. A process for the preparation of aninsecticidal fertilizer mixture comprising (a) mixing a compound of theformula ##STR12## with a fertilizer and an adhesive and optionallyadding disintegrants and surfactants and carriers and (b) compressing orextruding said mixture into a desired form.
 10. A method for theprotection of plants from unwanted insects which comprises adding aninsecticidally effective amount of the mixture according to claim 8 intothe nutrient medium of such plants.